Patent GB-948709-A (GB)
Title: Curable carboxyl containing polymers
IPC: C08L13/00
Filed: 1962-05-18
Abstract: Sulphide coated and phosphate coated polyvalent metal compounds such as the oxides and hydroxides of zinc, magnesium, cadmium, calcium, titanium, aluminium, barium, strontium, copper, cobalt and tin are prepared.  The sulphide coated oxide may be prepared by treating a granular solid zinc oxide with gaseous hydrogen sulphide (it may be diluted with an inert gas, e.g. nitrogen or oxygen) with hydrogen sulphide in a liquid medium such as water, with liquified hydrogen sulphide at low temperature or at pressures greater than atmospheric (less preferred) or finally with an organic sulphur compound such as a mercaptan RSH, where R is a hydrocarbon group having from 1 to 20 carbon atoms, all until the surface of the zinc oxide is converted to zinc sulphide.  The phosphate coatings include ortho-, meta-, ultra-, pyro-, poly-, monohydrogen- and dihydrogen-phosphates. The phosphate coated oxide may be prepared by treating a granular solid zinc oxide with a dilute aqueous solution of phosphoric acid or with a gaseous phosphoric oxide and steam or humid air without the use of a liquid diluent or less preferably with either liquid phosphoric acid, or an organic phosphate compound.  In examples: (1) 150 grams of dry particulate zinc oxide of varying average particle size are separately treated at 25 DEG  C. with a stream of hydrogen sulphide gas to give a colourless granular product.  The percentage of zinc sulphide in the product is 2.5 and 11.4 for 0.2 micron size particles, 0.14, 2.0 and 3.5 for 1.0 micron size and 1.8 and 6.25 for 1.5 micron size; (6) 81 grams of dry particulate zinc oxide of average particle size, 1 micron and 100 g. of water are agitated continuously at 25 DEG  C. while 0.72 g. of orthophosphoric acid is slowly added. Agitation is continued for a day and a product containing 2.65% zinc phosphate obtained. Similarly, zinc phosphate coated zinc oxides containing 3.9, 5.7, 7.8, 11.4 and 26.5% zinc phosphate are prepared.  Specification 707,425 and U.S.A. Specifications 2,303,329, 2,849,421 and 2,961,348 are referred to.ALSO:A curable composition comprises a major proportion of a plastic carboxyl containing polymer and a minor proportion of a sulphide or phosphate coated polyvalent metal compound. The polymer may be produced by copolymerising a mixture containing one or more carboxylic monomers, by polymerising monomers containing groups hydrolysable to carboxyl groups or by reacting a carboxylating agent with a polymer not containing carboxyl groups. Long lists of carboxyl containing monomers are given including alpha-beta unsaturated mono-di-and higher carboxylic acids e.g beta-benzol acrylic acid, maleic acid, sorbic aicd, 2-4-6-8-decatrienoic acid, acrylic acid methacrylic acid and their homologues, the acrylic and methacrylic esters, and the vinyl esters e.g. vinyl acetate. The non-carboxylic monomers include the conjugated dienes and substituted dienes butadiene being preferred. Specified polyvalent metal compounds are the oxide of zinc, magnesium, cadmium, calcium, titanium, aluminium, barium, strontium, copper(ic), cobalt(ic) and tin, the hydroxides of calcium, cadium, zinc, and barium and carboxylic acid salts of these metals.  The coated polyvalent metal oxides are preferred and zinc sulphide or zinc phosphate coated zinc oxide is most preferred.  The usual vulcanizing and compounding, ingredients e.g., carbon black, stearic acid, processing oil, sulphur mercaptobenzothiazole disulphide and tetramethyl thiuram disulphide may be present. The compositions may also be used in cements in which case the polymer and metal compound are milled together and then dissolved in methyl ethyl ketone. Examples use as polymers 67 butadiene-27 acrylo-nitrile-6 methacrylic acid and 92 butadiene- 8 methacrylic acid. Specification 707,425 and U.S.A. Specifications 2,303,329, 2,849,421 and 2,961,348 are referred to.